Diethyloctandioldicarbamates and diethyloctandioldiallophanates, method for the production and use thereof

ABSTRACT

The invention relates to positional isomer diethyloctandioldicarbamates and diethyloctandioldiallophanates, to a method for the production thereof and to the use thereof as synthetic building blocks and constituents of adhesives, luting compounds and coating materials.

[0001] The present invention relates to novel positionally isomericdiethyloctanediol dicarbamates and diethyloctanediol diallophanates. Thepresent invention further relates to novel processes for preparing thesenovel compounds. The present invention additionally relates to the useof these novel compounds as synthesis building blocks and asconstituents of adhesives, sealing compounds, and coating materials.Moreover, the present invention relates to novel adhesives, sealingcompounds, and coating materials which comprise the novel compounds. Thepresent invention further relates to novel adhesive films, seals, andcoatings which can be produced with the aid of the novel adhesives,sealing compounds, and coating materials. The present invention relatesnot least to novel primed and unprimed substrates which carry the noveladhesive films, seals, and/or coatings.

[0002] The patents U.S. Pat. No. 5,474,811, U.S. Pat. No. 5,356,669,U.S. Pat. No. 5,605,965, WO 94/10211, WO 94/10212, WO 94/10213, EP-A-0594 068, EP-A-0 594 071 and EP-A-0 594 142 disclose thermally curablecoating materials which comprise binders (in this respect, cf. RömppLexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York,1998, “Binders”, pages 73 and 74) containing at least one lateral and/orterminal carbamate group of the formula:

—O—(CO)—NH₂

[0003] and at least one crosslinking agent containing at least twofunctional groups which enter into crosslinking reactions with thecarbamate group. These known coating compositions provide clearcoatspossessing extremely high scratch and etch resistance. Crosslinkingagents employed are primarily highly etherified melamineformaldehyderesins. The crosslinking itself is acid catalyzed, with the catalystsused preferably being strong protic acids, especially sulfonic acids,which in general are blocked with amines.

[0004] Moreover, the European patent application 97122649.3-2102discloses thermally curable coating materials comprisingcarbamate-functionalized (cf. the formula above) amino resins. Thesecompounds are used as crosslinking agents for nonfunctionalized aminoresins or for binders containing lateral carbamate-reactive functionalgroups. The coating materials likewise provide coatings having very goodperformance properties.

[0005] These known, nitrogen-rich coating materials frequently have ahigh viscosity, which is detrimental to the application and leveling ofthe coating materials. There is therefore a need to lower the viscosityof the coating materials without having to reduce their solids content.There is also a need to increase further the proportion of thecomplementary reactive functional groups, especially the proportion ofthe carbamate groups or similar groups, which are needed for thermalcrosslinking. However, this should not involve any further increase inthe hydrophilicity of the coating materials and of the coatings, so asnot to reduce the already high level of acid resistance and moistureresistance.

[0006] In this context, the property of being hydrophilic refers to theconstitutional property of a molecule or of a functional group topenetrate the aqueous phase or to remain therein. For further details,reference is made to Römpp, op. cit., “Hydrophilicity”,“Hydrophobicity”, pages 294 and 295.

[0007] It is an object of the present invention to provide novelcarbamate-functional and/or allophanate-functional adhesives, sealingcompounds, and coating materials which may be cured thermally, orthermally and with actinic radiation (dual cure), and which no longerhave the disadvantages of the prior art but which instead, with a highsolids content and a high proportion of nitrogen-containing, thermallycrosslinking, complementary reactive functional groups, have acomparatively low viscosity and produce adhesives, sealing compounds,and coatings which have a high acid resistance and moisture resistance.

[0008] A further object of the present invention was to provide novelcompounds which are highly suitable constituents of adhesives, sealingcompounds, and coating materials that are curable thermally, orthermally and with actinic radiation.

[0009] Yet another object of the present invention was to provide novelcompounds which are able to function as synthesis building blocks inhigh-molecular and low-molecular organic chemistry and in organometallicchemistry.

[0010] The invention accordingly provides the novel positionallyisomeric diethyloctanediol dicarbamates and diethyloctanedioldiallophanates, referred to comprehensively below as the “compounds ofthe invention”.

[0011] The invention also provides novel processes for preparing thecompounds of the invention, which are referred to comprehensively belowas the “processes of the invention”.

[0012] The invention further provides the novel adhesives, sealingcompounds, and coating materials curable thermally, or thermally andwith actinic radiation, which comprise the compounds of the inventionand/or the compounds of the invention prepared with the aid of theprocesses of the invention and which are referred to below as the“adhesives, sealing compounds or coating materials of the invention”.

[0013] Furthermore, the invention provides the novel adhesive films,seals, and coatings which can be produced from the adhesives, sealingcompounds or coating materials of the invention and which are referredto below as the “adhesive films, seals or coatings of the invention”.

[0014] Further subject-matter of the invention will emerge from thefollowing description.

[0015] In the light of the prior art it was surprising for the skilledworker that the object on which the present invention is based might beachieved with the aid of the compounds of the invention. A particularsurprise in this context was the ready availability of the compounds ofthe invention and their extremely broad usefulness.

[0016] The compounds of the invention contain primary, secondary ortertiary carbamate groups or allophanate groups. In light of the use inthe adhesives, sealing compounds, and coating materials of theinvention, the primary and secondary carbamate groups and allophanategroups are of advantage and are therefore used with preference.Particular advantages, however, are afforded by primary carbamate groupsand allophanate groups, which accordingly are used with particularpreference in accordance with the invention.

[0017] The compounds of the invention contain a linear C8 carbon chain.

[0018] With regard to the two ethyl groups, the linear C8 carbon chainhas the following substitution pattern: 2,3, 2,4, 2,5, 2,6, 2,7, 3,4,3,5, 3,6 or 4,5. In accordance with the invention it is of advantage ifthe two ethyl groups are in positions 2 and 4, i.e., if the compoundsare 2,4-diethyloctanediol dicarbamates and 2,4-diethyloctanedioldiallophanates.

[0019] With regard to the two hydroxyl groups, the C8 carbon chain hasthe following substitution pattern: 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8,2,3, 2,4, 2,5, 2,6, 2,7, 2,8, 3,4, 3,5, 3,6, 3,7, 3,8, 4,5, 4,6, 4,8,5,6, 5,7, 5,8, 6,7, 6,8 or 7,8. In accordance with the invention it isof advantage if the two hydroxyl groups are in positions 1 and 5, i.e.,if the compounds are diethyloctane-1,5-diol dicarbamates ordiethyloctane-1,5-diol diallophanates.

[0020] The two substitution patterns are combined with one another inany desired way; i.e., the compounds of the invention comprise

[0021] 2,3-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0022] 2,4-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0023] 2,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0024] 2,6-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0025] 2,7-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0026] 3,4-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0027] 3,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0028] 3,6-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol, or

[0029] 4,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol dicarbamates or diallophanates.

[0030] Of these compounds of the invention, 2,4-diethyloctane-1,5-dioldicarbamate and 2,4-diethyloctane-1,5-diol diallophanate, but especially2,4-diethyloctane-1,5-diol dicarbamate, have particular advantages inthe context of their preparation and of their use, and so are used withparticular preference in accordance with the invention.

[0031] The preparation of the compounds of the invention starts from thepositionally isomeric diethyloctanediols.

[0032] The positionally isomeric diethyloctanediols for use inaccordance with the invention contain a linear C8 carbon chain whosesubstitution pattern determines the substitution pattern of thecompounds of the invention.

[0033] With regard to the two ethyl groups, the linear C8 carbon chainhas the following substitution pattern: 2,3, 2,4, 2,5, 2,6, 2,7, 3,4,3,5, 3,6 or 4,5. In accordance with the invention it is of advantage ifthe two ethyl groups are in positions 2 and 4, i.e., if the compoundsare 2,4-diethyloctanediols.

[0034] With regard to the two hydroxyl groups, the C8 carbon chain hasthe following substitution pattern: 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8,2,3, 2,4, 2,5, 2,6, 2,7, 2,8, 3,4, 3,5, 3,6, 3,7, 3,8, 4,5, 4,6, 4,8,5,6, 5,7, 5,8, 6,7, 6,8 or 7,8. In accordance with the invention it isof advantage if the two hydroxyl groups are in positions 1 and 5, i.e.,if the compounds are diethyloctane-1,5-diols.

[0035] The two substitution patterns are combined with one another inany desired way; i.e., the diethyloctanediols to be used in accordancewith the invention comprise

[0036] 2,3-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0037] 2,4-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0038] 2,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0039] 2,6-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0040] 2,7-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3, 8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0041] 3,4-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0042] 3,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol,

[0043] 3,6-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol, or

[0044] 4,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,-2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-, -3,7-,-3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-, -6,7-, -6,8- or-7,8-diol.

[0045] Particular advantages result from the use of2,4-diethyloctane-1,5-diol.

[0046] The positionally isomeric diethyloctanediols for use inaccordance with the invention are compounds which are known per se andthey can be prepared with the aid of customary and known synthesismethods of organic chemistry such as base-catalyzed aldol condensationor are obtained as by-products of large-scale chemical syntheses such asthe preparation of 2-ethylhexanol.

[0047] The compounds of the invention may be prepared in any desired,appropriate way in accordance with the customary and known methods oforganic chemistry, especially of organic nitrogen chemistry. Inaccordance with the invention, however, it is of advantage to preparethem in accordance with the processes of the invention.

[0048] The first process of the invention for preparing the positionallyisomeric diethyloctanediol dicarbamates of the invention comprises thereaction of the above-described positionally isomeric diethyloctanediolswith alkyl, cycloalkyl or aryl carbamates, especially methyl, butyl,cyclohexyl or phenyl carbamate, to give the positionally isomericdiethyloctanediol dicarbamates of the invention plus alcohols or phenolsas by-products. The by-products may be separated off in a customary andknown manner, by distillation, for example. Viewed in terms of itsmethod, the process of the invention has no special features but insteadis carried out along the lines of the methods and conditions describedin the patents U.S. Pat. No. 4,758,632, U.S. Pat. No. 4,310,257 and U.S.Pat. No. 2,979,514.

[0049] The second process of the invention for preparing thepositionally isomeric diethyloctanediol dicarbamates of the inventioncomprises the reaction of positionally isomeric diethyloctanediols withphosgene to give the corresponding positionally isomeric chloroformates.

[0050] Viewed in terms of its method, the preparation of thechloroformate-functional intermediates has no special features butinstead takes place in accordance with the customary and known methodsof phosgene chemistry, using the corresponding suitable equipment andtaking the safety measures which are customary for the handling ofphosgene.

[0051] Advantageously, the reaction with phosgene is conducted attemperatures of from −10 to 100, preferably from 0 to 50, and inparticular from 10 to 40° C., depending on the reactivity of thediethyloctanediols and/or on the stirability of the particular solutionof the diethyloctanediols.

[0052] Although the chloroformate-functional intermediates may beisolated as such, which may very well be of advantage for specificcases, it is generally advisable to react the intermediates in thesolution in which they are produced with ammonia and/or primary and/orsecondary amines.

[0053] Examples of suitable primary and secondary amines are those ofthe general formula I

NHRR¹   (I),

[0054] in which the variable R represents a hydrogen atom or representsmonovalent organic radical derived from the following compounds:

[0055] (i) substituted and unsubstituted, linear or branched alkanes,alkenes, cycloalkanes, cycloalkenes, alkylcycloalkanes,alkylcycloalkenes, alkenylcycloalkanes or alkenylcycloalkenes containingno or at least one heteroatom in the chain and/or in the ring;

[0056] (ii) substituted and unsubstituted aromatics or heteroaromatics;and also

[0057] (iii) alkyl-, alkenyl-, cycloalkyl-, cycloalkenyl-,alkylcycloalkyl-, alkylcycloalkenyl-, alkenylcycloalkyl- oralkenylcycloalkenyl-substituted aromatics or heteroaromatics whosesubstituents are substituted or unsubstituted and contain no or at leastone heteroatom in their chain and/or their ring;

[0058] and in which the variable R¹ has the meaning indicated above withthe exception of a hydrogen atom;

[0059] or in which the radicals R, with the exception of a hydrogenatom, and R¹ are linked cyclically with one another.

[0060] Examples of suitable heteroatoms are oxygen, nitrogen, boron,silicon, sulfur, and phosphorus atoms.

[0061] Examples of suitable substituents for the abovementioned radicalsR¹ are halogen atoms, especially fluorine and chlorine atoms, nitrogroups, and nitrile groups.

[0062] Examples of suitable aromatics are benzene and naphthalene.

[0063] Examples of suitable heteroaromatics are thiophene, pyridine, andtriazine.

[0064] Examples of suitable alkanes are those having 1 to 20 carbonatoms in the molecule such as methane, ethane, propane, butane,isobutane, pentane, neopentane, hexane, heptane, octane, isooctane,nonane, dodecane, hexadecane or eicosane.

[0065] Examples of suitable alkenes are ethylene and propylene.

[0066] Examples of suitable cycloalkanes are cyclopentane andcyclohexane.

[0067] Examples of suitable cycloalkenes are cyclopentene andcyclohexene.

[0068] Examples of suitable alkylcycloalkanes are methylcyclopentane andmethylcyclohexane.

[0069] Examples of suitable alkylcycloalkenes are methylcyclopentene andmethylcyclohexene.

[0070] Examples of suitable alkenylcycloalkanes are allyl- andvinylcyclopentane and allyl- and vinylcyclohexane.

[0071] Examples of suitable alkenylcycloalkenes are vinylcyclopenteneand vinylcyclohexene.

[0072] Examples of suitable alkyl, alkenyl, cycloalkyl, cycloalkenyl,alkylcycloalkyl, alkylcycloalkenyl, alkenylcycloalkyl andalkenylcycloalkenyl substituents are methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, vinyl, allyl, cyclohexyl, cyclohexenyl,4-methylcyclohexyl, 4-methylcyclohexenyl, 3-allylcyclohexenyl, and4-vinylcyclohexenyl.

[0073] The radicals R¹ are preferably derived from organic compoundswhich are unsubstituted per se or whose substituents are unsubstituted.

[0074] Advantageously, these compounds also contain no heteroatoms intheir chains and/or in their rings and/or in the chains and/or the ringsof their substituents.

[0075] Particular advantages result if the radicals R and R¹ are derivedfrom linear alkanes which meet the abovementioned advantageousconditions. Further advantages result if they are derived from methane,ethane, propane, butane, pentane or hexane.

[0076] Examples of highly suitable primary amines I are methylamine,ethylamine, propylamine, isobutylamine, hexylamine, cyclohexylamine,allylamine, cyclohexenylamine, aniline, cyclohexylmethylamine,(2-cyclohexyl)ethylamine and benzylamine.

[0077] Reaction with these primary amines I results in diethyloctanedioldicarbamates of the invention containing secondary carbamate groups.

[0078] Examples of highly suitable secondary amines I are dimethylamine,diethylamine, methylethylamine, dicyclohexylamine,methylcyclohexylamine, dibenzylamine, methylbenzylamine anddiphenylamine.

[0079] Examples of highly suitable cyclic amines I are imidazole,thiazine, morpholine, and piperidine.

[0080] Reaction with these secondary amines I results indiethyloctanediol dicarbamates of the invention containing tertiarycarbamate groups.

[0081] Since diethyloctanediol dicarbamates of the invention whichcontain primary carbamate groups are very particularly advantageous,ammonia is used with very particular preference in accordance with theinvention.

[0082] Viewed in terms of method, the reaction of ammonia and/or ofamines I with the chloroformate-functional intermediates has no specialfeatures but instead takes place in accordance with the customary andknown methods of organic chemistry. The equipment and techniques usedfor this purpose are guided in particular by whether solid, liquid orgaseous amines I or gaseous or dissolved ammonia are or is used. Theskilled worker will therefore be able to select the appropriatetechniques and equipment in a simple manner on the basis of his or herknowledge in the art.

[0083] The ammonium chlorides which are produced in the reaction of thechloroformate groups with ammonia or with the amines I are separatedfrom the reaction mixture, comprising the diethyloctanediol dicarbamateof the invention, in a customary and known manner. Examples of suitablemethods are filtration or extraction, it being possible to combine thesemethods with one another in an appropriate way.

[0084] The process of the invention for preparing the positionallyisomeric diethyloctanediol allophanates of the invention comprises thereaction of the positionally isomeric diethyloctanediols with alkyl,cycloalkyl or aryl allophanates, especially alkyl allophanates,particularly methyl or ethyl allophanate. In accordance with theinvention it is of advantage to conduct the reaction at from 50 to 150°C., preferably from 60 to 130° C., and in particular from 80 to 120° C.A particularly good reaction course is ensured if the alcohol and/orphenol are/is removed continually from the reaction mixture, bydistillation in vacuo, for example. In order to accelerate the reaction,a customary and known acidic catalyst such as p-toluenesulfonic acid mayalso be added to the reaction mixture.

[0085] Depending on the intended use, the compounds of the invention maybe isolated following their preparation and prior to their use, or elsethe solutions in which they are obtained may be used directly. Thepreferred variant is guided in particular by the intended use. Forinstance, in the context of their use in solventborne adhesives, sealingcompounds, and coating materials, the diethyloctanediol dicarbamates ofthe invention will be employed in solution, whereas prior to their usein solvent-free solid or liquid adhesives, sealing compounds and coatingmaterials they are isolated.

[0086] Because of their new kinds of structure, the compounds of theinvention may be used as valuable synthesis building blocks inlow-molecular and high-molecular organic chemistry and in organometallicchemistry.

[0087] The compounds of the invention may further be used for thepreparation of adhesives, sealing compounds, and coating materialscurable thermally and/or with actinic radiation. In particular, they areemployed as constituents of the adhesives, sealing compounds, andcoating materials of the invention. In this context, their proportion inthe adhesives, sealing compounds, and coating materials of the inventionmay vary extremely widely. Where the compounds of the inventionconstitute the principal constituent of the adhesives, sealingcompounds, and coating materials of the invention, their proportiontherein may preferably be up to 95, more preferably 90, with particularpreference 85, with very particular preference 80, and in particular 75%by weight, based in each case on the adhesives, sealing compounds orcoating materials of the invention. Alternatively, the compounds of theinvention may be employed as additives in the function of reactivediluents (in this regard, cf. Römpp, op. cit., “Reactive diluents”, p.491) for the thermal crosslinking. In this case, just a proportion ofpreferably from 0.1 to 20, more preferably from 0.2 to 18, withparticular preference from 0.3 to 16, with very particular preferencefrom 0.4 to 14, and in particular from 0.5 to 12% by weight, based ineach case on the adhesives, sealing compounds or coating materials ofthe invention, is sufficient to achieve the advantages of the invention.

[0088] The adhesives, sealing compounds or coating materials of theinvention may further comprise customary and known binders, crosslinkingagents, and additives in effective amounts.

[0089] The binders may come from any of a very wide variety of oligomerand polymer classes. Examples of suitable oligomer and polymer classesare random, alternating and/or block, linear and/or branched and/or combaddition (co)polymers of ethylenically unsaturated monomers, orpolyaddition resins and/or polycondensation resins. Regarding theseterms, reference is made for further details to Römpp, op. cit., page457, “Polyaddition” and “Polyaddition resins (polyadducts)”, and alsopages 463 and 464, “Polycondensates”, “Polycondensation”, and“Polycondensation resins”. As regards any substituents which may bepresent, the remarks made above apply accordingly.

[0090] Examples of highly suitable addition (co)polymers arepoly(meth)acrylates and partially saponified polyvinyl esters.

[0091] Examples of highly suitable polyaddition resins and/orpolycondensation resins are polyesters, alkyds, polyurethanes,polylactones, polycarbonates, polyethers, epoxy resin-amine adducts,polyureas, polyamides, and polyimides.

[0092] Particular advantages result if the above-described binderscontain carbamate-reactive functional groups such as N-methylol orN-methylol ether groups.

[0093] Examples of suitable crosslinking agents are amino resins.Examples of suitable amino resins are customary and known, and numerousproducts are available commercially.

[0094] Examples of highly suitable amino resins are melamine resins,guanamine resins, and urea resins. In this context it is possible to useany amino resin suitable for transparent topcoats or clearcoats, or amixture of such amino resins. For further details, reference is made toRömpp, op. cit., page 29, “Amino resins”, and the textbook“Lackadditive” [Additives for coatings] by Johan Bieleman, Wiley-VCH,Weinheim, N.Y., 1998, pages 242 ff., or to the book “Paints, Coatingsand Solvents”, second, completely revised edition, edited by D. Stoyeand W. Freitag, Wiley-VCH, Weinheim, N.Y., 1998, pages 80 ff. Alsosuitable are the customary and known amino resins some of whose methyloland/or methoxymethyl groups have been defunctionalized by means ofcarbamate or allophanate groups. Crosslinking agents of this kind aredescribed in the patents U.S. Pat. No. 4,710,542 and EP-B-0 245 700 andalso in the article by B. Singh and coworkers, “Carbamylmethylatedmelamines, novel crosslinkers for the coatings industry” in AdvancedOrganic Coatings Science and Technology Series, 1991, volume 13, pages193 to 207.

[0095] Besides these crosslinking agents, further crosslinking agentsmay also be present. Examples of suitable further crosslinking agentsare resins or compounds containing siloxane groups, resins or compoundscontaining anhydride groups, resins or compounds containing epoxidegroups, blocked and/or unblocked polyisocyanates, and/ortris(alkoxycarbonylamino)triazines, as described in the patents U.S.Pat. No. 4,939,213, U.S. Pat. No. 5,084,541, U.S. Pat. No. 5,288,865 andEP-A-0 604 922.

[0096] Depending on the reactivity of the further crosslinking agent, itmay be added directly to the coating materials, adhesives, and sealingcompounds of the invention to give what is known as a one-componentsystem. If, however, it is a particularly reactive crosslinking agent,such as a polyisocyanate or an epoxide, it is generally not added to thecoating materials, adhesives, and sealing compounds of the inventionuntil shortly before use. The result in this case is what is known as atwo-component or multicomponent system.

[0097] Where the coating materials, adhesives, and sealing compounds ofthe invention are to be curable not only thermally but also with actinicradiation, they include customary and known constituents which can beactivated with actinic radiation. In the context of the presentinvention actinic radiation means electromagnetic radiation, especiallyvisible light, UV light or X-rays, or corpuscular radiation, especiallyelectron beams. The use of UV light is particularly preferred. Examplesof suitable constituents which can be activated with actinic radiationare (meth)acryloyl-, allyl-, vinyl- or dicyclopentadienyl-functional(meth)acrylic copolymers or polyether acrylates, polyester acrylates,unsaturated polyester acrylates, epoxy acrylates, urethane acrylates,amino acrylates, melamine acrylates, silicone acrylates, or thecorresponding methacrylates.

[0098] Examples of suitable additives are crosslinking catalysts,initiators, in particular photoinitiators, pigments, dyes, fillers,reinforcing fillers, Theological aids, solvents, wetting agents,dispersants, defoamers, adhesion promoters, additives for improvingsubstrate wetting, additives for improving surface smoothness, flattingagents, leveling agents, film-forming auxiliaries, dryers, antiskinningagents, light stabilizers, corrosion inhibitors, biocides, flameretardents, polymerization inhibitors, especially photoinhibitors, orplasticizers, as customary and known, for example, in the plastics orcoatings sector. Further examples of suitable additives (C) aredescribed in the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH,Wienheim, N.Y., 1998.

[0099] The selection of the additives is guided by the desired profileof properties of the coating compositions, adhesives, and sealingcompounds of the invention and by their specific end uses and maytherefore be made by the skilled worker in a simple manner, possiblywith the assistance of simple preliminary tests.

[0100] The adhesives, sealing compounds, and coating materials of theinvention may be present in dispersion or solution in aqueous,aqueous-organic or organic media or may be present as a so-called NAD(non-aqueous dispersion). Furthermore, they may be present in finedivision in solid form, as powder coating materials, for example, or insolid forms dispersed in water, as powder slurries, for example.Moreover, they may be present in solvent-free liquid form, as what areknown as 100% systems. The constituents of the adhesives, sealingcompounds, and coating materials of the invention that are required ineach case are easy for the skilled worker to select on the basis of thegiven profile of properties (solid, liquid, soluble in organic solvents,water-soluble, etc.).

[0101] The preparation of the adhesives, sealing compounds, and coatingmaterials of the invention has no special features but instead takesplace in a customary and known manner by mixing of the above-describedconstituents in suitable mixing equipment such as stirred vessels,dissolvers, stirred mills, or extruders in accordance with the methodssuitable for the preparation of the respective adhesives, sealingcompounds, and coating materials of the invention.

[0102] The adhesives of the invention are used to produce adhesive filmsof the invention on primed and unprimed substrates.

[0103] The sealing compounds of the invention are used to produce sealsof the invention on and in primed and unprimed substrates.

[0104] The coating materials of the invention may be used asprimer-surfacers, solid-color topcoat materials, basecoat materials, andclearcoat materials and are used to produce single-coat or multicoatclearcoat systems or color and/or effect coating sytems on primed andunprimed substrates.

[0105] Very particular advantages result in the context of their use toproduce clearcoat systems, especially in the context of what is known asthe wet-on-wet technique, in which a basecoat material, in particular anaqueous basecoat material, is applied to the primed or unprimedsubstrate and dried but not cured, after which a clearcoat material isapplied to the basecoat film and the resultant clearcoat film is curedtogether with the basecoat film, thermally, or thermally and withactinic radiation.

[0106] Suitable coating substrates are all surfaces which are notdamaged by curing of the films present thereon using heat or acombination of heat and actinic radiation; examples of such substratesinclude metals, plastics, wood, ceramic, stone, textile, fibercomposites, leather, glass, glass fibers, glass wool, rock wool,mineral-bound and resin-bound building materials, such as plasterboard,cement slabs or roof tiles, and composites of these materials.Accordingly, the coatings, adhesive films or seals of the invention arealso suitable for applications outside of automotive OEM finishing andautomotive refinish. Here they are particularly suitable for thecoating, bonding and/or sealing of furniture and for industrialapplication, including coil coating, container coating, and theimpregnation or coating of electrical components. In the context of theindustrial applications, they are suitable for coating, bonding and/orsealing virtually all parts for private or industrial use, such asradiators, domestic applicances, small metal parts such as nuts andbolts, hubcaps, wheel rims, packaging, or electrical components such asmotor windings or transformer windings.

[0107] In the case of electrically conductive substrates it is possibleto use primers, which are produced in a customary and known manner fromelectrodeposition coating materials. For this purpose both anodic andcathodic electrodeposition coating materials are suitable, butespecially cathodic electrocoats.

[0108] It is also possible to coat, bond or seal primed or unprimedplastics parts made, for example, of ABS, AMMA, ASA, CA, CAB, EP, UF,CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC/PBT,PC/PA, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM,SMC, BMC, PP-EDPM, and UP (abbreviations in accordance with DIN 7728T1).Nonfunctionalized and/or nonpolar substrate surfaces may be subjectedprior to coating in a known manner to a pretreatment, such as with aplasma or by flaming, or may be provided with a water-based primer.

[0109] The application of the adhesives, sealing compounds, and coatingmaterials of the invention may take place by any customary applicationmethod, such as spraying, knife coating, brushing, flow coating,dipping, impregnating, trickling or rolling, for example. The substrateto be coated may itself be at rest, with the application equipment beingmoved. Alternatively, the substrate to be coated, especially a coil, maybe moved, with the application unit being at rest relative to thesubstrate or being moved appropriately. Where the adhesives, sealingcompounds, and coating materials of the invention include constituentswhich can be activated with actinic radiation, the application ispreferably carried out in the absence of light.

[0110] The applied films of the adhesives, sealing compounds, andcoating materials of the invention are cured thermally, or thermally andwith actinic radiation, in a customary and known manner, after allowingif desired a certain rest period which is used for leveling of the filmsand/or for the evaporation of volatile constituents.

[0111] In terms of its method, the thermal curing has no specialfeatures but instead the customary and known temperatures in the rangefrom room temperature up to 200° C., curing times in the range from oneminute to three hours, and equipment such as radiant heaters orforced-air ovens, are employed.

[0112] Curing with actinic radiation also has no special features interms of its method but instead takes place in a customary and knownmanner by irradiation with UV lamps and/or electron beam sources,preferably under inert gas.

[0113] In the context of the curing of the dual-cured adhesives, sealingcompounds, and coating materials of the invention, the thermal curingand curing with actinic radiation may be employed simultaneously oralternately. Where the two curing methods are used alternately, it ispossible, for example, to commence with thermal curing and to end withcuring-with actinic radiation. In other cases it may prove advantageousto commence with curing with actinic radiation and to end with it aswell. The skilled worker is able to determine the curing method mostadvantageous for the case in hand on the basis of his or her generalknowledge in the art, possibly with the assistance of simple preliminarytests.

[0114] The adhesive films and seals of the invention produced from theadhesives and sealing compounds of the invention possess outstandingbond strength and sealing capacity, even under extreme climaticconditions and over long periods of time.

[0115] The coatings of the invention produced from the coating materialsof the invention exhibit excellent leveling and have an outstandingoverall appearance. They are weathering-stable, acid-resistant andmoisture-resistant, and do not yellow even under tropical conditions.They can therefore be used both inside and outside.

[0116] Accordingly, the primed and unprimed substrates of the invention,especially bodies of automobiles and commercial vehicles, industrialcomponents, including plastics parts, packaging, coils and electricalcomponents, or furniture, which have been coated with at least onecoating of the invention, sealed with at least one seal of the inventionand/or bonded with at least one adhesive of the invention featureparticular technical and economic advantages, in particular a longservice life, so making them particularly attractive to users.

EXAMPLES Example 1

[0117] Preparation of 2,4-diethyloctane-1,5-diol dicarbamate

[0118] A 2 l glass apparatus with gas inlet tube, a brine condenser(−15° C.) and a dry-ice condenser was charged with 50 g of toluene andthis initial charge was saturated with phosgene at from 50 to 55° C.until a phosgene reflux set in. Thereafter, 4 g (2 mol) of2,4-diethyl-1,5-octanediol(hydroxyl number 536 mg KOH/g) in solution in808 g of toluene were reacted with a total of 480 g of phosgene at from50 to 55° C. over the course of 4 hours. Following a post-reactionperiod of 30 minutes at from 50 to 55° C., the reaction mixture wasstripped free of phosgene using nitrogen.

[0119] Subsequently, at from room temperature to 40° C., a total of 155g of gaseous ammonia was passed in over the course of 2.5 hours, forminga white precipitate of ammonium chloride. After the end of reaction, at70° C., 400 ml of water were added in order to separate off the ammoniumchloride. The aqueous phase was separated off at 70° C. and the organicphase was washed with twice 400 ml of water at 70° C. Subsequently, theorganic phase was concentrated on a rotary evaporator.

[0120] This gave 558 g (96.8%) of 2,4-diethyl-1,5-octanediol dicarbamatehaving a hydroxyl number of 27 mg KOH/g. The IR spectrum showed thecarbamate band as sole functional group.

Preparation Example 1

[0121] The Preparation of a Binder for Use in a Clearcoat Material ofthe Invention

[0122] An appropriate reaction vessel equipped with stirrer, refluxcondenser and two feed vessels was charged with 100 parts by weight of amixture of 2,4-diethyloctane-1,5-diol, methyl amyl ketone andethoxyethyl propionate (weight ratio: 1:1:1) and this initial charge washeated to 145° C. A mixture of 100 parts by weight of VeoVa® 10 (cf.Römpp, op. cit., “VeoVa®”, page 598), 150 parts by weight of styrene,100 parts by weight of tert-butylcyclohexyl acrylate, 200 parts byweight of n-butyl methacrylate, 10 parts by weight of 2-hydroxyethylacrylate and 100 parts by weight of isodecyl methacrylate was meteredinto the initial charge at a uniform rate over the course of 4.5 hourswith stirring. 15 minutes before the beginning of this feed stream, theaddition of a mixture of 40 parts by weight of di-tert-butyl peroxideand methyl amyl ketone was commenced. This mixture was metered into theresulting reaction mixture at a uniform rate over 5 hours. Followingpostpolymerization, the reaction mixture was adjusted usingmethoxypropyl acetate to a solids content of 74% by weight (one hour at130° C.).

Example 2

[0123] Preparation and Application of a Clearcoat Material of theInvention

[0124] 1 part by weight of 2,4-diethyloctane-1,5-diol dicarbamate (cf.example 1), 1 part by weight of a commercial melamine resin (Luwipal®066 from BASF Aktiengesellschaft), 121.62 parts by weight of the bindersolution from preparation example 1 and 0.28 part by weight of acommercial acidic crosslinking catalyst (Nacure® 4575) were mixed withone another. The resulting clearcoat material was applied to glass in awet film thickness of 100 μm and was cured at 130° C. for 30 minutes.The resulting clearcoat of the invention was clear, transparent,scratch-resistant and acid-resistant.

What is claimed is:
 1. Positionally isomeric diethyloctanedioldicarbamates and diethyloctanediol diallophanates.
 2. The positionallyisomeric diethyloctanediol dicarbamates and diethyloctanedioldiallophanates as claimed in claim 1, which contain primary carbamate orallophanate groups.
 3. The positionally isomeric diethyloctanedioldicarbamates and diethyloctanediol diallophanates as claimed in claim 1or 2, whose linear C8 carbon chain has the following substitutionpattern with regard to the two ethyl groups: 2,3, 2,4, 2,5, 2,6, 2,7,3,4, 3,5, 3,6 or 4,5.
 4. The positionally isomeric diethyloctanedioldicarbamates and diethyloctanediol diallophanates as claimed in claim 3,wherein the two ethyl groups are in positions 2 and
 4. 5. Thepositionally isomeric diethyloctanediol dicarbamates anddiethyloctanediol diallophanates as claimed in any of claims 1 to 4,whose C8 carbon chain has the following substitution pattern with regardto the two carbamate groups or allophanate groups: 1,2, 1,3, 1,4, 1,5,1,6, 1,7, 1,8, 2,3, 2,4, 2,5, 2,6, 2,7, 2,8, 3,4, 3,5, 3,6, 3,7, 3,8,4,5, 4,6, 4,8, 5,6, 5,7, 5,8, 6,7, 6,8 or 7,8.
 6. The positionallyisomeric diethyloctanediol dicarbamates and diethyloctanedioldiallophanates as claimed in claim 5, wherein the two carbamate groupsor allophanate groups are in positions 1 and
 5. 7. The positionallyisomeric diethyloctanediol dicarbamates and diethyloctanedioldiallophanates as claimed in claim 6, which are2,4-diethyloctane-1,5-diol dicarbamate and 2,4-diethyloctane-1,5-dioldiallophanate.
 8. A process for preparing positionally isomericdiethyloctanediol dicarbamates as claimed in any of claims 1 to 7 fromdiethyloctanediols, which comprises reacting positionally isomericdiethyloctanediols with alkyl, cycloalkyl or aryl carbamates.
 9. Aprocess for preparing positionally isomeric diethyloctanedioldicarbamates as claimed in any of claims 1 to 7 from diethyloctanediols,which comprises the reaction of positionally isomeric diethyloctanediolswith phosgene to give the corresponding chloroformates and reactingthese intermediates with ammonia and/or amines.
 10. A process forpreparing positionally isomeric diethyloctanediol diallophanates asclaimed in any of claims 1 to 7 from diethyloctanediols, which comprisesthe reaction of positionally isomeric diethyloctanediols with alkyl,cycloalkyl or aryl allophanates.
 11. The process as claimed in any ofclaims 8 to 10, wherein the linear C8 carbon chain of the positionallyisomeric diethyloctanediols has the following substitution pattern withregard to the two ethyl groups: 2,3, 2,4, 2,5, 2,6, 2,7, 3,4, 3,5, 3,6or 4,5.
 12. The process as claimed in claim 11, wherein the two ethylgroups are in positions 2 and
 4. 13. The process as claimed in any ofclaims 8 to 12, wherein the C8 carbon chain of the positionally isomericdiethyloctanediols has the following substitution pattern with regard tothe two hydroxyl groups: 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3, 2,4,2,5, 2,6, 2,7, 2,8, 3,4, 3,5, 3,6, 3,7, 3,8, 4,5, 4,6, 4,8, 5,6, 5,7,5,8, 6,7, 6,8 or 7,8.
 14. The process as claimed in claim 13, whereinthe two hydroxyl groups are in positions 1 and
 5. 15. The process asclaimed in claim 14, wherein 2,4-diethyloctane-1,5-diol is used.
 16. Theuse of the positionally isomeric diethyloctanediol dicarbamates anddiethyloctanediol diallophanates as claimed in any of claims 1 to 7, ofthe positionally isomeric diethyloctanediol dicarbamates prepared withthe aid of the process as claimed in any of claims 8, 9 and 11 to 15,and of the diethyloctanediol diallophanates prepared with the aid of theprocess as claimed in any of claims 10 to 15 as synthesis buildingblocks in low-molecular and high-molecular organic chemistry and inorganometallic chemistry.
 17. The use of the positionally isomericdiethyloctanediol dicarbamates and diethyloctanediol diallophanates asclaimed in any of claims 1 to 7, of the positionally isomericdiethyloctanediol dicarbamates prepared with the aid of the process asclaimed in any of claims 8, 9 and 11 to 15, and of the diethyloctanedioldiallophanates prepared with the aid of the process as claimed in any ofclaims 10 to 15 for the preparation of adhesives, sealing compounds, andcoating materials curable thermally, or thermally and with actinicradiation.
 18. Adhesives, sealing compounds and coating materialscurable thermally, or thermally and with actinic radiation, comprisingat least one of the diethyloctanediol dicarbamates and/or at least oneof the diethyloctanediol diallophanates as claimed in any of claims 1 to7 and/or at least one of the diethyloctanediol dicarbamates preparedwith the aid of the process as claimed in any of claims 8, 9 and 11 to15 and/or at least one of the diethyloctanediol diallophanates preparedwith the aid of the process as claimed in any of claims 10 to
 15. 19.Adhesive films, seals, and coatings on and in primed and unprimedsubstrates, which can be produced from the adhesives, sealing compounds,and coating materials, as claimed in claim 18, curable thermally, orthermally and with actinic radiation.
 20. Primed and unprimed substrateswith adhesive films, seals and/or coatings as claimed in claim 19.